Process for the manufacture of



'Y 55 ess the mayh m-neg: goli'v'eiioil Patented Feb. 25, 1936 smnss roa m mur' 'aofrm or DENSAH s owm- Jolef llnnfl and'lohannea Kuohenbucln- Kr'o-- dmm, Ger a salmon to I; G. Farbenlndustrle Aktlengeaellaomt, n

on-the-Main,

flobrawlngflffinlloaflon'inno'Q1553; p NorQ'IS-MA. l, 1932f The presentinvention concerns thejinianurac-i we de afl p od ct byica ns. phen s orderivatives thereoi to act-on-unsaturatediatty acids or derivatives thereof-in the presen q'oI-J boron fluoride, if desired or fwhile;

ploying a solvent.

In accordance with the invention fatty acids. as well as derivatives thereof,v iorei'z ample, esters, primarily the unsaturated higher" 10 fatty acids occurring as glycerides. in'thenatural I fats and oils, yield novel types of condensation products with phenols and derivativesthereoi by the action of boron fluoride; fiartlcularlysultableas starting materialsare,the 'drying'1atty;.oils: conversion products of iatt'yoils; for example; the products known. underthe name o! oils (stand oils), obtainableonpolymerlzatlon by heating, it desired orreq intlie -presence'ot a catalyst. can likewise application The reaction proceeds-'in'generalgniost dvan tageously atroom temperature,,but liighet' tem peratures can also be. restarted to; fl-When- -select-, inz'the appropriate reaction temperature-regard" should be had to the fact; that. atitoo: lowfa tomas perature solidification of? the "reaction vor one o! the componentsnia'ytake place and. con-Qv sequently the reactiomwouldi'comeyto'an end} while when employlngv high'a temperatureunder certain I conditions gelatinizatiou not thefatty" acid component jrnight, result, We{ have V obtained satisiactoryresiflts, ior example; within a e etr s 9W P changeof the, reaction niixturmmm 'a deep-1' 'oran gjefto v albrig'ht whom the" inorganic cOn' ut--;-"' I uentsareseparatedhy filtrationandthe In 1 some cases we havefliound it advantageous, 1 85 to carry out "thej'reaction in 'presence'ot'aninert solvent, i.'e. a' solvent,,virhich does not react under the prevailingcqnditionsi As such solvents J:

1 hydrocarbons, such as-ior example, benzine,'benzene, toluene, ylenc'a'g as'well as chloroform, 40 bon tetrachloride and thelilieg -can flnd applica tion. I

The condemamproceeas generally with. evo? lution oi heat. reactiomproduct distinuis m b mnlov' 'vflns 'm v. f i. y-gs. considerably lower pdine: rid-when ploying Ireef phenols L'as a rule by yhishriac t value. Dependin'g on the material and the conditions' oi condensatlonFthe j condensationproduct is obtained; in:.'the '-.torm oI a viscous liquid 5o or a pronouncedadhiesivef. "which.

drawn to threads, ora'sla rubber lilr Among theunsaturated -tatty acidsT. or- .;deriv atives thereotespoiallyadapted j of 'cresol. The 011 possesses the tollowl Mame-.5

Ace fyl, value "I ine i iifi tuiaiii'iats;ggn dummy propionate, xylenoibenzoate"and'the lilieniaybe v Specially referred .t I

1- .'Ihe-jfol l'owingjexamples willfi urtherillustratel the lr ventlon:f?. x I

e -M 2 n needinfthe'course of several hours by means oil a aicurrentiot nitrogen and while stirringv into .a 'mixture-'ot"300 grams of olive 011, (add value 1.3;

saponification value} 192.4; acetyl value- 18.5;

time at room temperature, =T'he mixturebeconies I and undecomposed 'cresol are" distilled oil; 1 The last' reinaining'gtraces'otfcresol are d'istilled1rom w 1 thereactionpr'oductat about 250. C'. under a m' s i t m a ww a a viscous oil are obtained, which doesjnotusmelli duced fin the course l f, 2647 non-r 2 4:

'eans r a' current or nitrogenTandwhile 09 39am Y c t n. vane 183 8: new:

such-ori {the Iormjofth mixtures 3 :phenolsand' 'dei'ivativesf thereof phenols;cziisiil 's; xylenolalnaphthols'fand halogen substitution {products ther'eoi' as well -asphenol]- v v ethersi and esters, 5 such as. {or example,- anisol;

phenetol; diphenylethefl;"phenylacetate,' cresol i *abo t 11.5.5 I or boron, made are I intro iodine-value 91.01) and grams. of'cresolniixshould be taken by cooling we... that the temperature does not rise above 45 C. The mixture slowly becomes viscous and assumes a deep orange red coloration. It is allowed to stand overnight, diluted with 200 grams of benzene and the boron fluoride is decomposed by the addition of 2.5 ccs. of water and 31.5 grams of sodium bicarbonate. After flltering the benzene and cresol are distilled from the mixture as indicated in Example 1. About 405 grams of a very viscous adhesive mass are obtained, which can be drawn to threads and possesses the following constants:-

Acid value 5.7

Saponiflcation value 150.8

Acetyi value 55 Iodine value 72.5

trample 8 about 210 C. under a pressure of 18 mms., when a small quantity of olelc acid distills 01!. About 365 grams of a viscous oil are obtained, which does not smell of cresol and which the following constants:

Acid value 98.6 Baponiflcation value -a 147.5 Acetyi value 55 Iodine value 43.6

' Immlc 4 About24gramsof boron fluorideareintrodueed withstirringinthecourseoflilhoursintoa mixtureoi'300gramsoftechnicallinseedoil fatty acid (acid value 180; saponiflcation value 215; acetyl value 7; iodine value 162) and 200 grams of cresol. The temperature rises slowly to about 45 C. and is maintained approximately constant by gentle cooling. During the introduction of the boron fluoride the dark brown reaction mixture becomes somewhat more viscous. The working up follows as described in Example 3. About 395 grams of a viscous linseed oil fatty acid-cresol condensation product are obtained, which can be drawn to threads and which does not smell of cresol. The product the following constants:

Acid value Saponiflcation value 142 Acetyl value 2 Iodine value 68 trample 5 About 18 grams of boron fluoride are intro duced in the course of 9 hours with stirring at room temperature-into a mixture of 300 grams of linseed oil for lacquer (constants as in Example2 and200gramsofanisole. Thetemperaturerisestoabout30'0. Themixtureisallowed Acid value v 5.5 Baponiflcation value Acetyl value 38.5 Iodine value 109 Methoxyl content 5.7%

It may be mentioned that instead of boron fluoride compounds of the same, for example, complex compounds, with organic acids, such as formiato-fluoro-boric acid, acetato-fluoro-boric acid, chloroacetato-fluoro-boric acid, lactatefluoro-boric acid. oleato-fluoro-boric acid, stearato-fiuoro-boric acid. can also be employed as the condensing agents in the process of this invention.

We claim:

1. The process which comprises reacting with material selected from the group consisting of phenols, chloro phenols, alkyl phenols, ethers of phenols and esters of phenols with monocarboxylic acids upon material selected from the group consisting of unsaturated fatty acids of fatty oils and natural fats. the glycerlne esters thereof,themixtures of these glycerineesters contained in the fatty oils and natural fats and furthermorestandoilsinthepresenceofboron fluoride.

2. The process which reacting with aphenoluponanunsaturatedfattyacidofa fatty oil in the presence of boron fluoride.

3. The process which comprises reacting wf'h linseedoilfattyaciduponcresolinthepresmee of boron fluoride at a temperature of about 45' C.

4. The process which comprises reacting with a phenol upon an ester of an umaturated fatty acidofafattyoiiinthepresenceofboron 5. The process which comprises reacting with eresoluponlinseedoilinthepruenceofboron fluoride at a, temperature of about 45 C.

6. 'Ihepmcesswhichcomprisesreactingwitha phenol ether upon a glycerine ester of an unsaturatedfattyacidofafattyoilinthepresenceof boron fluoride.

7. The process which comprises reacting with anisoleuponlinseedoilinthepresenceofboron fluoride at a temperature of about 50' C.

8. A condensation product obtainable by reacting with material selected from the group consisting of phenols, chloro phenols, alkyl phenols. ethers of phenols and esters of phenols with monocarboxylic acids upon material selected from the group consisting of unsaturated fatty acids of fattyoils and natural fats, the glycerine esters thereof, the mixtures of these glycerine esters contained in the fatty oils and natural fats and furthermore stand oils in the presence of boron fluoride, said product being distinguished from the starting material of fatty nature employed .by a considerably lower iodine value.

10. A condensation product obtainable by reacting with cresol upon linseed oil in the presence of boron fluoride at a temperature of about 45 C., said product having an acid value of 5.7, a saponiflcation value of 150.8, an acetyl value of 56 and an iodine value oi. 72.5.

11. A condensation product obtainable by reacting with a phenol ether upon a glycerine ester of an unsaturated fatty acid of a fatty oil in the presence of boron fluoride, said product being distinguished from the'glycerine ester or an unsaturated fatty acid of a fatty oil employed by a considerably lower iodine value.

12. A condensation product obtainable by reacting with anisole upon linseed oil in the presence of boron fluoride at a temperature of about 30, said product having an acid value of 6.5, a saponiflcation value of 175, an acetyl value of 38.5, an iodine value of 109 and a methoxy] content of 6.7.

JOSEF BINAPFL. JOHANNES KUCHENBUCH. 

